Discovering Electrochemical Cells

PGCC CHM 102 Sinex

Part I – Electrolytic Cells
Many important industrial processes

Cell Construction
e-

-

battery

+
e-

power source

conductive medium

vessel

(-)

(+)
inert electrodes

Sign or polarity of electrodes

What chemical species would be present in a vessel of molten sodium chloride, NaCl (l)?

Na+

Cl-

Let’s examine the electrolytic cell for molten NaCl.

Molten NaCl

Observe the reactions at the electrodes

-

battery

+

Cl2 (g) escapes Na (l) Cl(-)

Na+ ClCl-

NaCl (l) Na+ (+) Na+ electrode half-cell 2Cl-  Cl2 + 2e-

electrode half-cell Na+ + e-  Na

Molten NaCl

At the microscopic level

-

e-

battery

+

NaCl (l) cations migrate toward (-) electrode cathode Na+ + e-  Na anions migrate toward (+) electrode anode 2Cl-  Cl2 + 2e-

Cl(-)

Na+ Cl Cl-

Na+ e(+) Na+

Molten NaCl Electrolytic Cell
cathode half-cell (-) REDUCTION anode half-cell (+) OXIDATION Na+ + e-  Na 2Cl-  Cl2 + 2eX2

overall cell reaction 2Na+ + 2Cl-  2Na + Cl2
Non-spontaneous reaction!

Definitions:
CATHODE REDUCTION occurs at this electrode ANODE OXIDATION occurs at this electrode

What chemical species would be present in a vessel of aqueous sodium chloride, NaCl (aq)?

Na+ H 2O

Cl-

Will the half-cell reactions be the same or different?

Aqueous NaCl
e-

-

battery

+
e-

power source

NaCl (aq) What could be reduced at the cathode?

Na+ Cl-

cathode different half-cell

(-)

H2 O

(+) anode 2Cl-  Cl2 + 2e-

Aqueous NaCl Electrolytic Cell
possible cathode half-cells (-) REDUCTION Na+ + e-  Na 2H20 + 2e-  H2 + 2OHpossible anode half-cells (+) OXIDATION 2Cl-  Cl2 + 2e2H2O  O2 + 4H+ + 4eoverall cell reaction 2Cl- + 2H20  H2 + Cl2 + 2OH-

e-

For every electron, an atom of silver is plated on the electrode. Ag+ + e-  Ag Electrical current is expressed in terms of the ampere, which is defined as that strength of current which, when passed thru a solution of AgNO3 (aq) under standard conditions, will deposit silver at the rate of 0.001118 g Ag/sec

Ag+

Ag

1 amp = 0.001118 g Ag/sec

Faraday’s Law
The mass deposited or eroded from an electrode depends on the quantity of electricity. Quantity of electricity – coulomb (Q) Q is the product of current in amps times time in seconds
coulomb

Q = It

time in seconds

current in amperes (amp)

1 coulomb = 1 amp-sec = 0.001118 g Ag

Ag+ + e-  Ag
1.00 mole e- = 1.00 mole Ag = 107.87 g Ag 107.87 g Ag/mole e= 96,485 coul/mole e0.001118 g Ag/coul

mole e- = Q/F

1 Faraday (F )

mass = molemetal x MM
molemetal depends on the half-cell reaction

Examples using Faraday’s Law
• How many grams of Cu will be deposited in 3.00 hours by a current of 4.00 amps? Cu+2 + 2e-  Cu • The charge on a single electron is 1.6021 x 10-19 coulomb. Calculate Avogadro’s number from the fact that 1 F = 96,487 coulombs/mole e-.

• A series of solutions have 50,000 coulombs passed thru them, if the solutions were Au+3, Zn+2, and Ag+, and Au, Zn, and Ag were plated out respectively, calculate the amount of metal deposited at each anode. e- + battery +
e1.0 M Au+3 Au+3 + 3e-  Au

-

+
e-

-

+
e-

1.0 M Zn+2 Zn+2 + 2e-  Zn

1.0 M Ag+ Ag+ + e-  Ag

The Hall Process for Aluminum
• Electrolysis of molten Al2O3 mixed with cryolite – lowers melting point • Cell operates at high temperature – 1000oC • Aluminum was a precious metal in 1886. • A block of aluminum is at the tip of the Washington Monument!

graphite anodes

e- 

CO2 bubbles O-2 Al2O3 (l)

Al+3 O-2 Al (l)

from power source Al+3 O-2

+

 e-

-

carbon-lined steel vessel acts as cathode

Cathode: Al+3 + 3e-  Al (l) Anode: 2 O-2 + C (s)  CO2 (g) + 4e-

Draw off Al (l)

The Hall Process
Cathode: Al+3 + 3e-  Al (l)
x4

Anode: 2 O-2 + C (s)  CO2 (g) + 4e- x 3 4 Al+3 + 6 O-2 + 3 C (s)  4 Al (l) + 3 CO2 (g)
The graphite anode is consumed in the process.

Part II – Galvanic Cells
Batteries and corrosion

Cell Construction
Observe the electrodes to see what is occurring.

KCl in agar Provides conduction between half-cells

Salt bridge –

Cu

Zn 1.0 M ZnSO4

1.0 M CuSO4

What about half-cell reactions?

What about the sign of the electrodes?

+
cathode half-cell Cu+2 + 2e-  Cu Cu plates out or deposits on electrode

-

Why?

anode half-cell Zn  Zn+2 + 2eZn electrode erodes or dissolves

Cu

What happened at each electrode?

Zn 1.0 M ZnSO4

1.0 M CuSO4

Galvanic cell
• cathode half-cell (+) REDUCTION Cu+2 + 2e-  Cu • anode half-cell (-) OXIDATION

Zn  Zn+2 + 2e-

• overall cell reaction Zn + Cu+2  Zn+2 + Cu
Spontaneous reaction that produces electrical current!

Now for a standard cell composed of Cu/Cu+2 and Zn/Zn+2, what is the voltage produced by the reaction at 25oC?

Standard Conditions Temperature - 25oC All solutions – 1.00 M All gases – 1.00 atm

Now replace the light bulb with a volt meter.

+
cathode half-cell Cu+2 + 2e-  Cu

1.1 volts

anode half-cell Zn  Zn+2 + 2e-

Cu

Zn 1.0 M ZnSO4

1.0 M CuSO4

We need a standard electrode to make measurements against!
The Standard Hydrogen Electrode (SHE) 25oC 1.00 M H+ 1.00 atm H2
H2 input 1.00 atm

Half-cell 2H+ + 2e-  H2
EoSHE = 0.0 volts

Pt

inert metal

1.00 M H+

Now let’s combine the copper half-cell with the SHE Eo = + 0.34 v

+

0.34 v
anode half-cell H2  2H+ + 2eH2 1.00 atm

cathode half-cell Cu+2 + 2e-  Cu

KCl in agar

Cu

Pt

1.0 M CuSO4

1.0 M H+

Now let’s combine the zinc half-cell with the SHE Eo = - 0.76 v

-

0.76 v
cathode half-cell 2H+ + 2e-  H2
H2 1.00 atm

anode half-cell Zn  Zn+2 + 2e-

KCl in agar

Zn 1.0 M ZnSO4

Pt

1.0 M H+

Assigning the E

o

Write a reduction half-cell, assign the voltage measured, and the sign of the electrode to the voltage. Zn+2 + 2e-  Zn 2H+ + 2e-  H2 Cu+2 + 2e-  Cu Ag+ + e-  Ag Eo = - 0.76 v Eo = 0.00 v Eo = + 0.34 Eo = + 0.80 v
Increasing activity

Al+3 + 3e-  Al

Eo = - 1.66 v

The Non-active Metals
Metal + H+  no reaction since Eocell < 0

Db

105

107

Bh

Calculating the cell potential, Eocell, at standard conditions H2O with O2
Fe

Consider a drop of oxygenated water on an iron object Eo = -0.44 v reverse

Fe+2 + 2e-  Fe 2x

Fe  Fe+2 + 2e- -Eo = +0.44 v Eo = +0.40 v

O2 (g) + 2H2O + 4e-  4 OH-

2Fe + O2 (g) + 2H2O  2Fe(OH)2 (s) Eocell= +0.84 v This is corrosion or the oxidation of a metal.

Is iron an active metal?
Fe + 2H+  Fe+2 + H2 (g) Eocell = +0.44 V

What would happen if iron is exposed to hydrogen ion?
2x Fe  Fe+2 + 2e- -Eo = +0.44 v O2 (g) + 4H+ + 4e-  2H20 Eo = +1.23 v Eocell= +1.67 v

2Fe + O2 (g) + 4H+  2Fe+2 + 2H2O

How does acid rain influence the corrosion of iron?
Enhances the corrosion process

What happens to the electrode potential if conditions are not at standard conditions?
The Nernst equation adjusts for non-standard conditions For a reduction potential: ox + ne  red

atin general: = Eo = Eo – RT log(red) 25oC: E E - 0.0591 ln (red) n nF (ox) (ox) Calculate the E for the hydrogen electrode where 0.50 M H+ and 0.95 atm H2.

Free Energy and the Cell Potential
Cu  Cu+2 + 2e2x

-Eo = - 0.34 Eo = + 0.80 v Eocell= +0.46 v

Ag+ + e-  Ag

Cu + 2Ag+  Cu+2 + 2Ag

∆Go = -nFEocell
where n is the number of electrons for the balanced reaction What is the free energy for the cell?
1F = 96,500 J/v

from thermodynamics: ∆Go = -2.303RT log K and the previous relationship: ∆Go = -nFEocell -nFEocell = -2.303RT log K at 25oC: Eocell = 0.0591 log K n
where n is the number of electrons for the balanced reaction

Comparison of Electrochemical Cells
galvanic electrolytic

need produces power electrical two current electrodes source anode (-) conductive anode (+) cathode (+) medium cathode (-) salt bridge ∆G < 0 vessel ∆G > 0

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